Cysteamine permanent wave composition and method

ABSTRACT

A single formula, mild permanent wave reducing composition and method of permanently waving or reshaping human hair that provides a strong, long lasting curl and leaves the hair soft while minimizing further damage to already damaged hair. The composition contains a cysteamine reducing agent compound selected from the group consisting of cysteamine, a cysteamine salt, and mixtures thereof; and a second reducing agent selected from the group consisting of a monothioglycolate; an alkanolamine salt of thioglycolic acid; a thiolactic acid; a thioglycolic acid; thioglycerin; salts of thiolactic acid; cysteine; a salt of cysteine; a sulfite; a hyposulfite; and a bisulfite. The cysteamine compound should be present in an amount of about 7.8% to about 9% by weight; and sufficient additional alkali, if necessary, to bring the pH of the composition to about 7.8 to about 8.8. Unexpectedly, the composition is applied to any type of hair, regardless of structural damage to the hair, resulting in the same degree of curl tightness and softness and can be applied much more frequently than prior art permanent wave compositions without significant damage to the hair.

This is a continuation of U.S. application Ser. No. 08/111,305, filedAug. 24, 1993, now U.S. Pat. No. 5,362,487 which is acontinuation-in-part of U.S. application Ser. No. 07/819,113 filed Jan.10, 1992 now U.S. Pat. No. 5,260,054.

FIELD OF THE INVENTION

The present invention is directed to a permanent wave lotion compositioncontaining a combination of reducing agents, including cysteamine, andmethod for relatively permanently reshaping or curling human hair into alasting curl pattern. More particularly, the present invention isdirected to a composition and method capable of forming a "permanent"wave in human hair such that regardless of the condition of the hair,i.e., whether it be substantially undamaged or normal hair, tinted hair,frosted hair, bleached hair or hair substantially damaged as a result ofsome other prior hair treatment or environmental condition, thecomposition will permanently reshape both normal and damaged hair tosubstantially the same extent without the danger of overprocessing.Significantly, the composition does not require a compound added for thepurpose of establishing an equilibrium reaction with the reducing agent,e.g., a dithioglycolate, such as diammonium dithioglycolate, to preventoverprocessing of and damage to the hair. Further, the composition canbe applied repeatedly to the hair without significant damage so that thehair can be permed at least every 3 to 6 weeks to maintain a freshlooking perm without significant damage.

BACKGROUND OF THE INVENTION

In general, permanent waving of human hair is achieved by chemicallybreaking the sulfur to sulfur or disulfide cystine bonds occurringnaturally in human hair and then reforming the cystine bonds while thehair is wrapped or curled on rods. The sulfur to sulfur cystine bonds inhuman hair maintain the hair in a naturally straight or curlyconfiguration and, in order to permanently reshape the hair into alasting, different configuration, a significant percentage of the sulfurto sulfur bonds must be broken and then reestablished after the hair isreconfigured in a desired position, such as wrapped around a suitablemandrel or roller. In general, the sulfur to sulfur cystine bonds arebroken with a composition containing a reducing agent and after the hairis wound into a curl formation around a rod or roller, the sulfur tosulfur cystine bonds are relinked or reestablished while the hair is inthe curl formation by contacting the hair in the new formation with anoxidizing agent, such as hydrogen peroxide or a water-soluble bromate.

As set forth in German Offen. DE 3,631,991, others have used a reducingagent composition that is a combination of cysteamine, or its salts,together with a monothioglycolic acid ester for permanent hair waving(see CA Selects: Cosmetic Chemicals, Issue 1, 1989, 109: 236730h). Alsoan N-acylcysteamine HSCH₂ CH₂ NHCOR(R=2-10 C alkyl)., as a hair reducingcompound, has been used together with another reducing agent selectedfrom the group consisting of cysteine, acidic sodium hyposulfite, sodiumsulfite, thioglycerol and thiolactic acid, as disclosed in JapanesePatent JP63146808. Similarly, published European Patent Application88306449.5, publication number 0299764, discloses the use of cysteamineas a reducing agent together with sulfite, bisulfite and disulfidecompounds, such as cystamine, to effect reoxidation. The use ofcystamine, as an oxidizing agent in the permanent waving process, isdisclosed in Siuta-Mangano U.S. Pat. No. 4,795,629. Japanese publishedPatent Application No. 2053-714-A discloses cysteamine together with adithioglycolate stop action compound. These patents and publications,however, do not recognize the use of cysteamine as a reducing agent inthe concentration and at the pH disclosed herein, or that cysteaminealone, or in combination with one or more additional reducing agents, atthe cysteamine concentration and pH ranges disclosed herein, provides anessentially constant aggressivity with time.

The reducing action of mercaptans on keratin is due mostly to thedissociated form of the thiol groups, the thiolate anion. Acid permanentwaves sufficiently curl hair at a lower pH compared to alkalinepermanents because the waving agents in these permanents have low pKavalues and thus exist predominantly in dissociated (thiolate) form at apH near neutral, or slightly acidic pH. Hence, the pKa value shows thatsome mercaptans are efficient at high pH while others with a low pKavalue and high ionization constant are efficient at lower pH values. Forexample, it is well known that the alkaline salts of thioglycolic acid,e.g., the ammonium salt of thioglycolic acid (pKa=10.4) has acceptablewaving efficiency only if the pH of solution exceeds 9, see Zviak,Charles, The Science of Hair Care, Permanent Waving and HairStraightening, p. 191, 1986; while amides such as thioglycolamide(pKa=8.4), and esters such as glycerol thioglycolate (pKa=7.8) giveacceptable waving efficiency at neutral and even slightly acid pH.

The cysteamine-based reducing agent-containing composition and method ofthe present invention includes a second reducing agent compound selectedfrom the group consisting of a monothioglycolate; an alkanolamine saltof thioglycolic acid; a thiolactic acid; a thioglycolic acid;thioglycerin; salts of thiolactic acid; cysteine; a salt of cysteine; asulfite; a hyposulfite; and a bisulfite, and is unexpectedly effectivein the pH range of about 7.8 to about 8.8 and particularly in the pHrange of about 8 to 8.5, without increasing hair damage or otherwiseadversely affecting the benefits of a cysteamine reducing agent withinthe aforementioned pH and concentration ranges.

Different reducing agents are effective to break the cystine bonds thatcross link human hair protein at the different pHs. Generally speaking,the acid permanent wave compositions having a lower pH include reducingagents such as bisulfites, e.g., ammonium bisulfite, or glycerolmonothioglycolate, capable of breaking the sulfur to sulfur cystinebonds within lower pH ranges, whereas the alkaline permanent wavecompositions, having pHs in the range of about 7.5 to 9.5, require analkaline salt of thioglycolic acid - so that the alkali can penetrateand swell the hair shaft for easier penetration of the reducing agent inorder to break the sulfur to sulfur cystine bonds.

The use of diammonium dithiodiglycolate in acid or alkaline permanentwave lotions allows greater flexibility in processing time because itminimizes the possibility of overprocessing. This is due to the factthat the reaction of thioglycolic acid (TGA) with hair keratin is anequilibrium process. Thus by including diammonium dithiodiglycolate(oxidized TGA) in the wave lotion, the rate of the reaction of thethioglycolic acid with hair keratin is decreased and prevented fromgoing to completion.

Generally, the permanent wave compositions of the prior art do notinclude moisturizers, such as glycerine, since moisturizers cause lossof curl, as disclosed in Cannell et al. U.S. Pat. No. 4,301,820.

One of the biggest problems associated with the permanent waving processis due to human error in the person applying the permanent wavinglotion. If the reducing agent is applied to the hair shaft for the wrongperiod of time, too many or too few of the sulfur to sulfur bonds in thehair shaft are broken, resulting in seriously damaged hair or resultingin hair which has not been sufficiently treated to achieve a permanentwave with long lasting potential. Some of the reasons that the personapplying the permanent wave composition has difficulty in determiningthe correct amount of time for processing is that the reducing agentreaction in breaking the sulfur to sulfur bonds is dependent upon theamount of heat applied to the hair; the amount of time the reducingagent is in contact with the hair; the concentration of reducing agent;the pH of the lotion applied; and the condition of hair.

Perhaps the most difficult factor for the applier of the permanent wavelotion to assess in determining how long to apply the reducing agent tothe hair is the condition of the hair at the time of the permanent wave.It is well documented in the literature and prior art that the hair canbe damaged by abuse of chemicals, e.g., by shampooing, permanent waving,tinting, frosting, bleaching, and particularly any hair treatmentinvolving the use of hydrogen peroxide; mechanical treatment, e.g.,thermal appliances; and environmental conditions, e.g., climate andpollution. It is well known that damaged hair, depending upon the stageand degree of damage of the hair, has significantly different chemicalactivity to reducing agents than normal or undamaged hair. If too manyof the sulfur to sulfur bonds in the hair are broken by the reducingagent, the hair will be seriously weakened and may disintegrate.

It is theorized that somewhere in the range of about 20% to about 60% ofthe natural sulfur to sulfur cystine bonds in the hair shafts should bebroken in order to give the hair the capability of being reshaped to anydesired shape, such as curled around a rod or roller, and capable ofretaining this shape. If too few of the sulfur to sulfur bonds arebroken, the natural or normal configuration of the hair willpredominate, causing the hair to retain its previous shape. This isbecause the predominant prior or natural bonds in the hair dictate thatthe hair will remain in the old configuration or shape. Hydrogen bondsare physically broken when wet hair is stretched and wrapped around aroller. When the hair is dried, the hydrogen bonds are reformed in acurled position or shape. While the hydrogen bonds aid to maintain thehair in the new configuration, the sulfur to sulfur cystine bonds aremuch stronger and, to a much greater extent than the hydrogen bonds,control the efficacy of the permanent wave.

In order to successfully provide a satisfactory permanent wave in thehair, the sulfur to sulfur cystine bonds reformed in the hair in the newor curled configuration, when the hair is later oxidized with theneutralizing agent, should be stronger than the prior or natural cystinehair bonds. It is desired, therefore, when permanent waving, that enoughnew bonds in a new hair configuration are formed during permanent wavingto outweigh the number of old bonds remaining that tend to form the hairin its prior or natural configuration, whether it be straight ornaturally curled.

Since damaged hair already has a significant number of the sulfur tosulfur cystine bonds broken due to some chemical, mechanical orenvironmental abuse, particularly the chemical abuses, such asbleaching, tinting or frosting, it is difficult to determine what lengthof time, and what reducing agent concentration to apply to the hair toprovide the hair with the proper number of sulfur to sulfur bondsremaining after the reducing agent treatment. Significantly damagedhair, such as tinted hair, may require a reducing agent lotionapplication for a period of only about 5 minutes whereas a normal hair,not significantly damaged, may require the reducing agent lotion for aperiod of approximately 20 minutes under the same reducing agentconcentration and temperature in order to result in both the damaged andnormal hair having approximately the same curl configuration. Ideally,after the reducing agent treatment, every one of the hair shafts treatedwill contain the same ratio of broken to unbroken bonds so that thissame ratio can be re-established in each hair shaft when the hair is inthe new configuration to provide a consistent strong curl over theentire head of hair.

Generally, the reducing agent lotion is applied to the hair by firstshampooing the hair and then applying the reducing agent lotion to thehair, either before or after the hair is wrapped around suitablerollers. Since it is not possible for even the experienced permanentwave applier to accurately determine visually the extent of damage tothe hair in order to have a better idea of how long the reducing agentshould be in contact with the hair, it is necessary to take a "testcurl" so that after a predetermined amount of time, for example 10minutes, a first roller is removed from the hair and the curl is feltand stretched in an attempt to determine if the curl formation is strongenough. Once it is determined that the reducing agent has been incontact with the hair for a sufficient time period, the hair is rinsedthoroughly with water while still on the rollers or rods and, while thehair remains on the rollers or rods, a neutralizing agent is applied tooxidize and reform the sulfur to sulfur bonds while the hair is in thenew, rolled configuration. The neutralizing agent contains an oxidizingagent, such as hydrogen peroxide or a bromate salt, in order toreestablish the sulfur to sulfur bonds to leave the hair in a relativelypermanent, e.g., 2-4 months, new configuration. The rods are removed,before or after rinsing out the neutralizing agent.

When the reducing agent lotion is applied to sections of the head priorto rolling that portion of the hair onto the rods it is called a lotionwrap whereas when the hair is rolled on the rods or rollers first andthen the lotion applied onto all of the hair after rolling, this iscalled a water wrap. The timing for the reducing agent to be in contactwith the hair for a lotion wrap is begun from the time that all rods areon the head, and the timing for a water wrap begins from the time thatthe lotion application is completed. The capability of using a waterwrap is clearly more desirable since the lotion is applied to the entirehead of hair all at once in a short period of time and can be rinsedfrom the hair all at once to provide a more uniform reducing agentcontact time for all of the hair.

Other prior art patents directed to permanent waving compositionsintended to permanently wave both normal and damaged hair are found inthe Klemm et al. U.S. Pat. No. 4,273,143; and Cannel et al. U.S. Pat.No. 4,301,820. Japanese Patent No. 57-212110 appears to be directed to apost-permanent treatment containing glycerine to give hair sheen andluster.

Japanese published application No. 55-136857 teaches thatcysteamine-based permanent waving compositions are more effective withthioglycolic acid reducing agents, but does not disclose the cysteaminepH and concentration of the present invention, or the essentiallyconstant aggressivity disclosed herein.

In accordance with the present invention, a cysteamine-based permanentwave composition, containing a thioglycolate or thioglycolic acid, isprovided in a single formula which can be applied in a singlepredetermined amount of time to the hair, regardless of the structure ofthe hair, whether it be damaged or not, and this composition is capableof being water wrapped or lotion wrapped without the use of a dryer,hair caps or other heat treatment to speed the reducing agent action.

Prior art alkaline compositions containing a salt of thioglycolic acidas a reducing agent are known to produce a tight curl but leave the hairfeeling harsh due to the high alkalinity content. Prior art acid wavecompositions containing glycerol monothioglycolate as a reducing agentrequire the mixing of the reducing agent into a separate lotionimmediately prior to use since glycerol monothioglycolate will hydrolyzein contact with water and, therefore, must be kept separate untilimmediately prior to use. Further, the acid wave compositions generallyrequire heat to help swell the hair for reaction with the reducing agentsince the hair is not normally swelled sufficiently at the low pH of theacid wave compositions. The cysteamine-based reducing agent compositionsof the present invention include a second reducing agent compoundselected from the group consisting of a monothioglycolate; analkanolamine salt of thioglycolic acid; a thiolactic acid; athioglycolic acid; thioglycerin; salts of thiolactic acid; cysteine; asalt of cysteine; a sulfite; a hyposulfite; and a bisulfite. Thepreferred second reducing agent is a monothioglycolate, such as ammoniumthioglycolate (ATG), or an alkanolamine salt of thioglycolic acid, suchas monoethanolamine thioglycolate. The cysteamine-based reducingagent-containing permanent wave compositions of the present inventionsolve the above mentioned prior art deficiencies while being capable ofeffective permanent waving on hair, regardless of its extent of damageand regardless of the amount of time that the reducing agent composition(waving lotion) is left in contact with the hair.

SUMMARY OF THE INVENTION

In accordance with the present invention, the performance of acysteamine-based reducing agent formulation is further improved by theaddition of a second reducing agent, particularly ammonium thioglycolate(ATG), without increasing hair damage or otherwise adversely effectingthe benefits previously seen with cysteamine formulations.

Cysteamine has been shown to provide good curl and leave hair inexcellent condition when pH and concentration are tightly controlled.Attempts to increase curl formation by raising the pH or concentrationof cysteamine did not yield successful results because cysteamineexhibits a peak effect at a pH of 8.3 and a concentration of 8.3% byweight. At this concentration and pH, cysteamine formulations were shownto be non-damaging to hair and the aggressivity of the lotion did notchange appreciably over time, giving the hair stylist more flexibilityon processing time.

In brief, the present invention is directed to a single formula, mildpermanent wave reducing composition and method of permanently waving orreshaping human hair that provides a strong, long lasting curl, andleaves the hair soft, while minimizing further damage to already damagedhair. Generally, the composition contains a cysteamine reducing agentcompound selected from the group consisting of cysteamine; a cysteaminesalt, e.g., cysteamine hydrochloride, cysteamine chlorohydrate,cysteamine acetate, cysteamine phosphate, cysteamine nitrate, cysteaminebromide or cysteamine floride; and mixtures thereof; a second reducingagent selected from the group consisting of a monothioglycolate; analkanolamine salt of thioglycolic acid; a thiolactic acid; athioglycolic acid; thioglycerin; salts of thiolactic acid; cysteine; asalt of cysteine; a sulfite, a hyposulfite; and a bisulfite. In thepreferred embodiment, the cysteamine compound should be present in anamount of about 7.8% to about 9%, preferably about 7.8% to about 8.8% byweight; the second reducing agent can be included in an amount in therange of about 0.1% to about 18% by weight of the composition; and thereducing agent composition should include sufficient additional alkali,if necessary, to bring the pH of the composition to about 7.8 to about8.8, preferably about 8 to about 8.5. Optionally, a hair softeningand/or moisturizing agent, such as glycerine is included in thecomposition in an amount of about 0.1% to about 20% by weight,preferably about 0.1% to about 15% by weight of the composition.

This cysteamine-based multiple reducing agent-containing composition iseasy to use and apply and includes a second reducing agent, such as amonothioglycolate; an alkanolamine salt of thioglycolic acid; athiolactic acid; a thioglycolic acid; thioglycerin; salts of thiolacticacid; cysteine; a salt of cysteine; a sulfite; a hyposulfite; and abisulfite second reducing agent, without damaging the hair whileproviding a strong, tight curl and leaving the hair unexpectedly soft.The composition can be lotion or water wrapped and can be used with orwithout heat. Unexpectedly, the composition is applied to any type ofhair, regardless of structural damage to the hair, resulting in the samedegree of curl tightness and softness and can be applied much morefrequently than prior art permanent wave compositions withoutsignificant damage to the hair.

Accordingly, an aspect of the present invention is to provide a new andimproved permanent wave composition capable of breaking sulfur to sulfurbonds in human hair so that the hair can be reconfigured in a differentconfiguration. The sulfur to sulfur human hair bonds can bereestablished with an oxidizing agent to maintain the new hairconfiguration for a substantial time period.

Another aspect of the present invention is to provide a new and improvedpermanent wave lotion containing multiple reducing agents, including acysteamine reducing agent and a second reducing agent, preferably amonothioglycolate, wherein the multiple reducing agent-containing wavelotion is capable of breaking sulfur to sulfur hair bonds withoutcausing further significant damage to tinted, frosted, bleached or othersubstantially damaged hair.

Another aspect of the present invention is to provide a new and improvedcysteamine-based permanent wave reducing agent composition that includesa second reducing agent, such as a monothioglycolate; an alkanolaminesalt of thioglycolic acid; a thiolactic acid; a thioglycolic acid;thioglycerin; salts of thiolactic acid; cysteine; a salt of cysteine; asulfite; a hyposulfite; and a bisulfite that is capable of breakingsulfur to sulfur human hair bonds leaving normal and damaged hair withapproximately the same ratio of broken to unbroken sulfur to sulfurbonds when contacted with the composition for the same time period sothat the same degree of curl tightness can be achieved in both normaland damaged hair.

Another aspect of the present invention is to provide a permanent wavereducing agent-containing composition including a hair softening andmoisturizing agent that enhances the curl achieved with the composition.

These and other aspects and advantages of the present invention willbecome apparent from the following detailed description of the preferredembodiment.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph showing the activity of ammonium thioglycolate (ATG)versus time;

FIG. 2 is a graph showing the activity of cysteamine versus time;

FIG. 3 is a graph showing the activity of a cysteamine-based wavinglotion without a second reducing agent, in comparison to acysteamine-based waving lotion containing a second, monothioglycolate(ATG) reducing agent;

FIG. 4 is a graph showing the change in liquid retention of tinted hairwaved one time and three times with acid (GMT), alkaline (ATG) andcysteamine waving lotions; and

FIG. 5 is a graph showing the change in liquid retention of normal hairwaved one, two and three times with an alkaline (ATG) waving lotion incomparison to normal hair waved once with cysteamine at differentconcentrations, and compared to normal hair waved once with the alkalinewaving lotion and a second time with cysteamine.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention is directed to a permanent wave compositioncapable of permanently waving both damaged and undamaged hair in asingle formulation, water-wrap, applied for a constant processing timeas a mild permanent that produces a tight, long lasting curl formationand can be applied frequently without significant hair damage. Thecapability of permanently waving both damaged and undamaged hairrepeatedly with a single formulation in a single processing time withoutrequiring a test curl, without causing further damage to the hair, istotally unique in the industry and removes the opportunity for errorfrom the person applying the permanent wave lotion.

The composition of the present invention is a single formula, mild,alkaline permanent wave conditioning composition capable of waving orreshaping human hair and provides a strong, long lasting curl withoutfurther damaging already damaged hair. Generally, the compositioncontains a cysteamine compound selected from the group consisting ofcysteamine; a cysteamine salt, such as cysteamine hydrochloride,cysteamine chlorohydrate, cysteamine acetate, cysteamine phosphate,cysteamine nitrate, cysteamine bromide or cysteamine fluoride; andmixtures in an amount of about 7.8% by weight to about 9% by weight,particularly about 8% to about 8.5% by weight; and a second reducingagent, selected from the group consisting of a monothioglycolate; analkanolamine salt of thioglycolic acid; a thiolactic acid; athioglycolic acid; thioglycerin; salts of thiolactic acid; cysteine; asalt of cysteine; a sulfite; a hyposulfite; and a bisulfite.

In a preferred embodiment, the waving lotion has a pH in the range ofabout 8 to about 8.5 and a cysteamine concentration of about 8% to about8.5% by weight, and particularly about 8.3 for both pH and concentration(% by weight). Preferably, the reducing composition also includes a hairmoisturizer and/or softener selected from a polyhydroxyl alkyl compound,a polyalkylene glycol glycerol ether, an ethoxylated fatty alcohol, afatty alcohol polymerized either, and mixtures thereof in an amount ofabout 0.1% to about 20% by weight, particularly about 0.1% to about 15%by weight.

Examples of second reducing agents useful in accordance with the presentinvention are as follows. A monothioglycolate, including the preferredammonium thioglycolate (ATG), as well as potassium thioglycolate, andsodium thioglycolate. A salt of thiolactic acid, such as ammoniumthiolactate. Alkanolamine salts of thioglycolic acid, such asethanolamine thioglycolate, and methanolamine thioglycolate. Theseadditional (second) reducing agents can be combined within the wavinglotion, together with cysteamine, to provide any number of reducingagents, in addition to cysteamine. The total concentration of additionalreducing agents, other than cysteamine, should be in the range of about0.1% to about 18% by weight of the composition. It is preferred that thetotal concentration of additional reducing agents, other thancysteamine, is in the range of about 1% to about 10% by weight, morepreferably about 2% to about 6% by total weight of the waving lotioncomposition.

Optionally, the composition of the present invention includes aconditioner to improve the combing and manageability of the hair.Particularly, suitable conditions are the polymeric quaternary ammoniumsalts, such as Polyquaternium 1 through Polyquaternium 14, inclusive,conditioners defined on page 245, CTFA Cosmetic Ingredient Dictionary,Third Edition, 1982, hereby incorporated by reference. The preferredconditioners are Polyquaternium-4, Polyquaternium-10 andPolyquaternium-11. The conditioner, when added, is included in an amountof about 0.01% to about 2% by weight of the composition.

Other common cosmetic additives can be incorporated into the compositionof the present invention, as long as the basic properties of thepermanent wave composition are not substantially adversely affected.These additives include, but are not limited to, commonly usedfragrances, dyes, opacifiers, pearlescing agents, thickeners, foamstabilizers, preservatives, water softening agents, acids, bases,buffers and the like; and will usually be present in weight percentagesof less than about 1% each, and about 2% to about 5% in total. Thecomposition vehicle is predominantly water but organic solvents also canbe added to the composition in order to solubilize compounds that arenot sufficiently soluble in water. Suitable solvents include the loweralcohols, such as ethanol and isopropanol and mixtures. These solventscan be present in the hair setting composition of the present inventionin an amount from about 1% to about 75% by weight and in particular fromabout 5% to about 50% by weight, based on the total weight of thecomposition.

The composition optionally can be thickened, for example, with sodiumalginate, gum arabic, cellulose derivatives such as methylcellulose,hydroxyethylcellulose, hydroxypropylmethylcellulose andcarboxymethylcellulose, and various polymeric thickeners, such asacrylic acid derivatives. It is also possible to use inorganicthickeners, such as bentonire. These thickeners, when included,preferably are present in an amount from about 0.1% to about 10% byweight and, in particular, from about 0.5% to about 3% by weight, basedon the total weight of the composition.

The composition has a pH in the range of about 7.8 to about 8.8,preferably about 7.8 to about 8.5. To achieve the full advantage of thepresent invention, the composition has a pH of about 8 to 8.3 for bestcurl retention when cold waved. This pH can be achieved by the additionof an alkanolamine, ammonia, an ammonium carbonate, or a metal hydroxideto the composition of the present invention.

Moisturizers enhance the curl formation of the permanent wavecomposition of the present invention. The use of polyhydric alcohols orpolyhydroxy alkane compounds, such as ethylene glycol, glycerine,propylene glycol, or polyoxyethylene glyceryl ether in this compositionleave the hair in better condition due to humectant properties andsurprisingly does not compromise curl formation, but provides the hairwith a more uniform and natural curl.

These moisturizers are selected from the group consisting ofpolyhydroxyalkyl compounds, particularly alkylene glycols andpolyalkylene glycols, and especially ethylene glycol and thepolyethylene glycols; propylene glycol and the polypropylene glycols;polyethylene glycol glyceryl ethers; ethoxylated fatty alcohols; andfatty alcohol polyglycol ethers. Examples of suitable moisturizersinclude glycols and triols such as glycerine, ethylene glycol, propyleneglycol, 1,3-butylene glycol, 1,2,6-hexanetriol, 1,5-pentanediol,2-methyl pentanediol-2,4, and 2-ethyl hexanediol-1,3. Further examplesof suitable moisturizers include the polyalkylene glycols, such as thosecompounds having the formula ##STR1## wherein R is H or CH₃, and n hasan average value of 2 to 600; when R═H, particularly suitablemoisturizers have n in the range of 4 to 600; and when R═CH₃,particularly suitable moisturizers have n in the range of 2 to 34. Thepolyalkylene glycols that can be used as moisturizers in the permanentwave composition of the present invention are exemplified by, but notlimited to, compounds such as polyethylene glycol 200; polyethyleneglycol 400; polyethylene glycol 600; polypropylene glycol 150;tetraethylene glycol; and dipropylene glycol.

Examples of other suitable moisturizers include the polyethylene glycolglyceryl ethers, such as polyethylene glycol 600 glyceryl ether andpolyethylene glycol 26 glyceryl ether. Furthermore, the ethoxylatednonyl phenols and ethoxylated octyl phenols, particularly nonoxynol, C₉H₁₉ C₆ H₄ (OCH₂ CH₂)_(n) --OH, wherein n averages at least 6 and up toabout 100; and octoxynol, C₈ H₁₇ S₆ H₄ (OCH₂ CH₂)_(n) --OH, wherein naverages at least 7 and up to about 40, also are suitable moisturizersfor use in the composition of the present invention. Suitableethoxylated fatty alcohols for use as moisturizers in the composition ofthe present invention include compounds having the formula R--(OCH₂CH₂)_(n) OH, wherein R is an alkyl group containing from about 12 toabout 30 carbon atoms and n averages at least 6. In addition, fattyalcohol polyglycol ethers having the formula ##STR2## wherein R is analkyl group containing from about 8 to about 18 carbon atoms, n=0 to 6,m=0 to 6, and n+m is at least 6, also are useful as moisturizers in thecomposition of the present invention.

The composition of the present invention is easy to use and apply,repeatedly, without damaging the hair while providing a strong, tightcurl and leaving the hair unexpectedly soft. The composition can belotion or water wrapped and can be used with or without heat.Unexpectedly, the composition is applied to any type of hair, regardlessof structure damage to the hair, resulting in the same degree of curltightness and softness.

It is most surprising in the art that the composition of the presentinvention is capable of treating both normal and damaged hair, such astinted hair, in a single formula, using a non-critical processing timefor both normal and damaged hair and requires neither a test curl todetermine the processing time nor a dryer to fix the processing timewhile capable of repeated applications without significant hair damage.

The following data, in Table I and FIG. 3, illustrate the levelling ofaggressiveness of the hybrid cysteamine-based waving lotions of thepresent invention, in comparison to cysteamine as a sole reducing agent.

                  TABLE I                                                         ______________________________________                                        PERCENT CHANGE IN AGGRESSIVITY                                                FACTOR OVER TIME                                                                                     Average Reading                                        Waving Lotion                                                                              Reading at                                                                              Between      %                                         (weight %)   5 mins.   25-30 mins.  Change                                    ______________________________________                                        8.3% CYSTEAMINE                                                                            28.11     38.33        36.38                                     5% ATG                                                                        pH 8.3                                                                        8.3% CYSTEAMINE                                                                            29.51     39.05        32.36                                     10% ATG                                                                       pH 8.3                                                                        8.3% CYSTEAMINE                                                                            20.55     32.06        56.02                                     0% ATG                                                                        pH 8.3                                                                        ______________________________________                                    

Hair damage can be measured analytically in the laboratory by atechnique called Liquid Retention. The principle involved in the LiquidRetention test is based on the fact that damaged hair becomes moreporous and absorbs more moisture. The greater the amount of moisturepicked up by the hair, the greater the damage. There should be nosignificant increase in the amount of moisture picked up by hair that iswaved one time and three times with a waving lotion containing acombination of cysteamine and a second reducing agent, such as ammoniumthioglycolate. However, with the acid and alkaline waved hair, themoisture pick up after three wavings is significantly greater than onetime waved hair, as shown in FIGS. 4 and 5.

Hair damage also can be measured using an "Aggressivity factor" test asdescribed in TECHNOLOGIE et SCIENCE en COSMETOLOGIE (COSMETIC TECHNOLOGYand SCIENCE) "PREPRINTS - ORAL COMMUNICATIONS", Volume II, pp. 391-406(see p. 397), IFSSC Conference, Paris, 13-17 Sep. 1982, herebyincorporated by reference. In the "Aggressivity factor" test, with ATGand glycerylmonothioglycolate (GMT) at a constant concentration, when pHis varied, as shown in FIG. 1 for ATG, the Aggressivity factor increaseswith time, indicating that the damage done to the hair is progressivelyworse. Similarly, when the pH is kept constant and the concentration isvaried, hair damage gets progressively worse.

With the cysteamine-containing hybrid waving lotions of the presentinvention, the Aggressivity factor levels off within a relatively narrowcysteamine pH and concentration range and is not as linear as for thesecond reducing agents used alone. This levelling of the Aggressivityfactor indicates that damage to the hair does not get worse when hair isexposed to increasing concentrations or pH of the hybrid waving lotionwhen cysteamine is included in the waving lotion at a concentration ofabout 7.8% to about 9% by weight and the pH of the hybrid composition isin the range of about 7.8 to about 8.8.

With ATG and GMT alone, increasing the pH or concentration increases thenumber of reduced sites on the hair. With cysteamine and a secondreducing agent, for example, ammonium thioglycolate, there issubstantially little or no change in aggressivity with increasedconcentration of the second reducing agent, as shown in FIG. 3.

As shown in FIG. 1, when the pH of ATG is raised from 7 to 8 to 8.5 to9, its aggressivity increases and statistically these curves aresignificantly different from each other. The concentration of ATG in thewaving lotion of FIG. 1 was kept constant at 9%.

As shown in FIG. 2, cysteamine alone, at a pH of about 8.3 and aconcentration of about 8.3% by weight, provides an essentially constantAggressivity factor, in comparison to ATG. The following Table II alsoshows that cysteamine alone reaches a maximum (although essentiallyconstant) aggressivity at a concentration of about 8.3% by weight and apH of about 8.3.

                  TABLE II                                                        ______________________________________                                        MULTIPLE RANGE ANALYSIS                                                       FOR AGGRESSIVENESS FACTOR                                                             Average        Cysteamine                                             Count   Aggressivity   wt. %     pH                                           ______________________________________                                        60      27.32          8.3%      7.3 pH                                       60      28.68          8.3%      7.8 pH                                       60      29.81          7.8%      8.3 pH                                       60      30.73          8%        8.3 pH                                       60      32.36          9.8%      8.3 pH                                       60      32.60          9%        8.3 pH                                       60      33.48          8.3%      8.8 pH                                       60      33.81          8.3%      8.3 pH                                       ______________________________________                                    

As shown in FIG. 3, a hybrid waving lotion containing both ATG andcysteamine has an activity (Aggressivity factor) that is essentiallyconstant with time, like that of cysteamine alone, but has an increasedaggressivity for better curl formation. As shown in FIG. 3, the increasein aggressivity in a hybrid waving lotion containing 10% ATG, comparedto a hybrid waving lotion containing 5% ATG, is not substantial.Therefore, low concentrations, e.g., about 1% to about 6% by weight ATG,together with cysteamine at about 7.8% to about 9% by weight, and at awaving lotion pH of about 7.8 to about 8.8, provides a waving lotionhaving an aggressivity that is essential constant after about 5 minutesof contact time, e.g., 5-30 minutes or more, while providing excellentwaving efficiency (tight curl formation). Similarly, within cysteaminemolar concentrations of 0.60 to 0.80, the waving efficiencies ofcysteamine, together with a second reducing agent, are essentiallyconstant and do not significantly increase.

As shown in FIG. 3, a substantial increase in cysteamine aggressivity isobtained by including a relatively small concentration of a secondreducing agent, such as ammonium thioglycolate. It is expected that thehybrid waving lotions of the present invention will be capable ofproviding repeated permanent waves without substantial increase in hairdamage, as shown for cysteamine alone in FIGS. 4 and 5, in comparison toATG alone (IMPACT R), and GMT alone (QUANTUM X) in FIG. 4; and incomparison to ATG alone in FIG. 5.

FIG. 5 shows the damage caused by a waving lotion containing cysteamineas the only reducing agent on normal (undamaged) hair and previouslypermed hair in comparison to damage caused by a conventional alkaline(ATG-containing) waving lotion (IMPACT® waving lotion). As shown in thefirst three bars of the graph, the cysteamine-containing composition,used once, caused relatively little damage to normal (undamaged) hairover varying pHs and concentrations within the specified ranges, incomparison with IMPACT® waving lotion used one time (4th bar). Thefourth and fifth bars of FIG. 5 show that the damage to hair waved oncewith IMPACT® waving lotion and then a second time with a cysteaminewaving lotion is essentially the same as the damage caused by a singleperm with IMPACT® waving lotion (the second perming with the cysteaminewaving lotion caused essentially no additional damage). The last twobars of FIG. 5 show the extensive additional damage caused by a secondand third perming with IMPACT® waving lotion, respectively, that isfound in repeated perms with all other known, comparablecommercially-available waving lotions.

These unexpected findings, with cysteamine and a second reducing agent,namely, constant performance over a relatively narrow pH andconcentration range, led to the discovery of further benefits formultiple reducing agent cysteamine-based waving lotions. Withconventional waving agents, it is well known in the art to change theconcentration and/or pH when waving hair with different degrees ofdamage. For example, when preparing a formula for bleached hair,formulators will lower the aggressiveness of the active ingredient bylowering its pH or concentration. Since the performance of cysteamine,together with a second reducing agent, does not change over theabove-described narrow pH and concentration range, a single compositionhaving the same formula (without changing concentration or pH) can beused to permanently wave normal hair (relatively undamaged), bleachedhair, tinted hair, frosted hair and other damaged hair. Accordingly, thehybrid waving lotion of the present invention, containing widely varyingamounts of a second reducing agent, such as ammonium thioglycolate, willwave normal, tinted and bleached hair without causing excessive damageto tinted or bleached hair.

Further, hair can be repeatedly permed with a waving lotion containingcysteamine and a second reducing agent in accordance with the principlesof the present invention.

Without being bound to any particular theory, cysteamine, within theconcentration and pH ranges shown below, has some unexpected properties,namely, minimal damage and good curl efficacy. This may be attributed tothe amine functionality of the molecule.

The preferred composition is as follows:

    ______________________________________                                        FORMULATION          % W/W                                                    ______________________________________                                        Cysteamine HCl       7.8-9,                                                                        preferably 8.3                                           Ammnonium Hydroxide  q.s. to pH 7.8-8.8,                                                           preferably 8.3                                           Ammonium Thioglycolate                                                                             0.1-18%,                                                                      preferably 2-6%                                          Nonoxynol-15         0.90                                                     (Igepal CO-730)                                                               (fragrance solubilizer)                                                       Fragrance            0.30                                                     Water                q.s. to 100                                              ______________________________________                                    

Actual waving lotion compositions, having a preferred pH of 8.3 wereprepared using the above formula including 0%, 5% and 10% ATG, togetherwith 8.3% by weight cysteamine, as shown in FIG. 3.

The invention described herein is a further improvement in that the curlformation is increased by the addition of a second reducing agent while,at the same time, maintaining the other benefits of the cysteaminereducing agent.

It has been found that the aggressivity of cysteamine wave lotions canbe increased by the addition of a second reducing agent, such asammonium thioglycolate (see FIG. 3). One unexpected finding is that theaggressivity increases to the essentially same extent regardless of theamount of second reducing agent, e.g., ammonium thioglycolate, that isadded to the cysteamine-based waving lotion. Another surprising findingis that in hybrid formulations, the aggressivity levels off even fasterthan when cysteamine was used alone. As shown by the data in Table I,the hybrid waving lotion approaches its essentially constantaggressivity faster than when using cysteamine alone (see reading at 5minutes versus reading at 25-30 minutes or % change), making the time ofwaving lotion contact with the hair even less critical than forcysteamine alone.

The hybrid, multiple reducing agent-containing waving lotions of thepresent invention represent an improvement over cysteamine formulationswithout a second reducing agent, such as ammonium thioglycolate, sincethe hybrid waving lotions maintain all the advantages of cysteamine at ahigher curl performance level, with even less criticality in processingtime.

Many modifications and variations of the invention as hereinbefore setforth can be made without departing from the spirit and scope thereofand, therefore, only such limitations should be imposed as are indicatedby the appended claims.

What is claimed is:
 1. A permanent wave composition capable of breakingsulfur to sulfur bonds in human hair when in contact with said humanhair so that said hair can be reconfigured in a predeterminedconfiguration, comprising an aqueous solution of a cysteamine in anamount of at least about 7.8% by weight of the permanent wavecomposition and in an amount sufficient, at the pH of the composition,to provide cysteamine thiolate anions in solution in a concentration ofat least about 0.2 Molar to about 0.6 Molar; and a second reducing agentin an amount of about 0.1% to about 18% by weight of the composition. 2.The composition of claim 1, wherein the second reducing agent isselected from the group consisting of a monothioglycolate; analkanolamine salt of thioglycolic acid; a thiolactic acid; athioglycolic acid; thioglycerin; salts of thiolactic acid; cysteine; asalt of cysteine; a sulfite; a hyposulfite; and a bisulfite.
 3. Thecomposition of claim 2, wherein the second reducing agent is amonothioglycolate.
 4. The composition of claim 3, wherein themonothioglycolate is selected from the group consisting of ammoniumthioglycolate, potassium thioglycolate, sodium thioglycolate, andmixtures thereof.
 5. The composition of claim 4, wherein themonothioglycolate is ammonium thioglycolate.
 6. The composition of claim1 further including a polyhydric moisturizer selected from the groupconsisting of polyhydroxyalkyl compounds; polyalkylene glycols; glycerylether compounds; ethoxylated fatty alcohols; ethoxylated alkyl phenols;fatty alcohol polyglycol ether compounds; and mixtures thereof.
 7. Thecomposition of claim 1, wherein the cysteamine is included in an amountof about 7.8% to about 8.7% by weight of the composition.
 8. Thecomposition of claim 7, wherein the cysteamine is cysteaminehydrochloride.
 9. The composition of claim 6, wherein the moisturizer isglycerine or a polyalkylene glycol ether of glycerine having an averageethoxylation value of 5 to
 50. 10. The composition of claim 1 furtherincluding a quaternary ammonium conditioning compound in an amount ofabout 0.1% to about 2% by weight of the composition.
 11. The compositionof claim 1, wherein the cysteamine is included in the composition in aconcentration of about 0.60 to about 0.80 molar.
 12. The composition ofclaim 1, wherein the second reducing agent is included in thecomposition in an amount of about 1% to about 10% by weight of thepermanent wave composition.
 13. The composition of claim 12, wherein thesecond reducing agent is included in the composition in an amount ofabout 2% to about 6% by weight of the composition.
 14. A method ofbreaking sulfur to sulfur bonds in human hair to leave the hair weakenedso that it can be reconfigured to a predetermined configuration, whileminimizing further damage to damaged hair, including contacting the hairfor a predetermined amount of time with an aqueous permanent wavecomposition comprising at least about 7.8% by weight of a cysteamine andin an amount sufficient, at the pH of the composition, to providecysteamine thiolate anions in solution in a concentration in the rangeof about 0.2 Molar to about 0.6 Molar; the composition and a secondreducing agent in an amount of about 0.1% to about 18% by weight of thepermanent wave composition; forming the hair in a desired configurationsuch that the hair is in contact with the permanent wave compositionwhile formed in the new configuration; and then removing most of thepermanent wave composition from the hair.
 15. The method of claim 14,wherein the second reducing agent is selected from the group consistingof a monothioglycolate; an alkanolamine salt of thioglycolic acid; athiolactic acid; a thioglycolic acid; thioglycerin; salts of thiolacticacid; cysteine; a salt of cysteine; a sulfite; a hyposulfite; and abisulfite.
 16. The method of claim 15, wherein the second reducing agentis a monothioglycolate.
 17. The method of claim 14, wherein the secondreducing agent is included in the composition in an amount of about 1%to about 6% by weight of the composition.
 18. The method of claim 17,wherein the monothioglycolate is ammonium thioglycolate.
 19. The methodof claim 14 further including wrapping a plurality of human hairsections around a plurality of mandrels to reconfigure the hair sectionsin a plurality of curl configurations such that the hair iscurl-configured while in contact with the reducing agent-containingcomposition; and removing the mandrels sequentially after saidpredetermined time period without testing the hair from one of the firstremoved mandrels for curl tightness.
 20. The method of claim 14 whereinthe composition includes a polyhydric moisturizer in an amount of about0.1% to about 20% by weight of the composition.
 21. The method of claim20, wherein the polyhydric moisturizer is selected from the groupconsisting of polyhydroxyalkyl compounds; polyalkylene glycols; glycerylether compounds; ethoxylated fatty alcohols; ethoxylated alkyl phenols;and fatty alcohol polyglycol ether compounds; or mixtures thereof. 22.The method of claim 14, wherein the cysteamine is included in an amountof about 8% to about 8.7% by weight of the composition.
 23. The methodof claim 22, wherein the pH is about 8.3 and the concentration of thecysteamine is about 8.3% by weight.
 24. The method of claim 14, whereinthe second reducing agent is included in the composition in an amount ofabout 2% to about 5% by weight of the composition.
 25. The compositionof claim 1, wherein the concentration of the cysteamine is in the rangeof about 7.8% to about 9.0% by weight of the composition.
 26. Thecomposition of claim 1, wherein the concentration of the cysteamine isin the range of about 0.71 Molar to about 0.82 Molar.
 27. The method ofclaim 14, wherein the aqueous permanent wave composition includes thecysteamine in a concentration in the range of about 7.8% to about 9.0%by weight.
 28. The method of claim 14, wherein the aqueous permanentwave composition includes the cysteamine in a concentration in the rangeof about 0.71 Molar to about 0.82 Molar.